Define sensitivity - 應用非均勻矽鍺奈米線在生物感測器上提升其靈敏度

Chapter 2. Experiment

2.4 Define sensitivity

In this study, we define sensitivity is that : S =∣I - I⁰∣/ I⁰ , where I⁰ is the current of V^D = -8V, when nanowire has not dipped APTMS yet; I is the current of V^D = -8V, when nanowire has dipped APTMS.

This method is as same as : S=∣G - G⁰∣/ G⁰ (chapter 1.8), because I^D-V^D curve is a line.

Chapter 3 7 percent Ge of SiGe nanowire sensors

3.1 Cross-section view : 7 percent Ge of SiGe nanowires

Si⁹³Ge⁷ nanowires were successfully fabricated by sidewall spacer formation. Fig. 3-1 is the SEM images of Si⁹³Ge⁷. The height is about 128 nm and the width is about 62 nm.

The Si⁹³Ge⁷ nanowire is p-type which is doped BF², 10¹⁵ ions/cm² and implantation energy is 50 KeV.

3.2 Defined sensitivity after dipped APTMS

We select that the current at V^D = -8V is a baseline. For instance, the length of Si⁹³Ge⁷ nanowire is 4um. Before dipped APTMS, the current is -154.2uA at V^D= -8V; after dipped APTMS, the current change to -141.48uA. Therefore, sensitivity is :

S=∣[(-141.48uA)-(-154.2uA)] / (-154.2uA)∣= 8.249% , shown in Fig. 3-2.

3.3 Procedure of forming non-homogeneous SiGe nanowire

For performing non-homogeneous SiGe nanowire, We utilize Ge condensation technique to make the outer layer with high Ge distribution. As a result, the outer layer is high conductance. Thus, we can get non-homogeneous structure.

First, we oxidize Si⁹³Ge⁷ nanowire with three different temperatures (850℃, 900℃

and 950℃) and post-annealing in pure N² ambient at 900℃ for 30 minutes. The procedure chart show in Fig. 3-3.

The aim of annealing is that it can repair defects after oxidation. One of pre-work is annealing condition in our group. Fig. 3-4, shows that annealing at 900℃ for 30 minutes gets better conductance change, so we still follow this condition [24].

In this experiment, we perform three different oxidation temperatures with different oxidation time, and discussing the effect of temperature and time on the sensitivity.

3.4 Comparing sensitivity between uniform and non-homogeneous SiGe nanwire

Box chart, Fig. 3-5, shows oxidizing Si⁹³Ge⁷ nanowire at 850℃ for 0, 3 and 5 minutes. Box chart in the middle has a quadrangle. If there are a group data, the 75 percent value from little to large means the upper line of the box chart, and the 50 percent and 25 percent value mean the middle and lower line of the box chart, respectively. The point in the middle quadrangle means the group data’s mean value.

Via Fig. 3-5, the mean value is 7.8119% without oxidation. After oxidation at 850℃

for 3 minutes, the mean value is 8.7493%. Moreover, oxidation at 850℃ for 5 minutes, the mean value is 9.6674%. The trend is that sensitivity promote along with oxidation time.

And then, we want to know that temperature affects sensitivity of SiGe nanowire, so we promote oxidation temperature 50℃; that is 900℃.

Fig. 3-6, shows that the mean value is 7.8119% without oxidation. After oxidation at 900℃ for 3 minutes, the mean value is 9.7711%. Furthermore, oxidation at 900℃ for 5 minutes, the mean value is 12.0689%. Via these results, we also can get the trend.

Sensitivity is promoting along with oxidation time at 900℃.

To go on, we add oxidation temperature 50℃ again; that is, oxidation temperature fixed at 950℃.

When no oxidizing, the mean sensitivity is 7.8119%, and the mean sensitivity is 13.5381% after oxidation at 950℃ for 3 minutes. However oxidation at 950℃ for 5 minutes, the mean sensitivity is degrading to 10.4265%, shown in Fig. 3-7.

Although oxidation makes Ge concentration promoting in the surface, it also makes defects. We know that it is two mechanism of oxidation of SiGe. One is Ge concentration piling up in the outer layer, so sensitivity increases. The other is that oxidation makes defects, so sensitivity decreases. When oxidation time at 950℃ from 3 to 5 minutes, the sensitivity degrades, we guess that the effect of defects is more dominant than Ge concentration promoting on the outer surface of nanowire.

In this study, we need to control oxidation temperature and time to get balance between defects generation and Ge piling up in the outer layer of nanowire.

Oxidation temperature is also a important factor. When we fix oxidation time for 3 minutes, comparing with three oxidation temperatures which are 850℃, 900℃ and 950℃, we gets a trend. Sensitivity promotes along with temperature. It accounts for when oxidation temperature from 850℃ to 950℃, Ge concentration is not enough, so the sensitivity is promoting, shown as Fig. 3-8.

To continue, we fixed oxidation temperature for 5 minutes, comparing with three oxidation temperatures which are 850℃, 900℃ and 950℃, shown as Fig. 3-9. When oxidation temperature from 850℃ to 900℃, sensitivity promotes, because at 900℃ Ge piling up in outer layer’s velocity is faster than 850℃. However, oxidation temperature from 900℃ to 950℃, sensitivity decreases, and we guess that defects generation at 950℃

are more than 900℃.

Via Fig. 3-10, in these conditions, the best condition is oxidation at 950℃ for 3 minutes, and the sensitivity is 13.5381%. Comparing with uniform Si⁹³Ge⁷ nanowire, whose sensitivity is 7.8119%. Subtracting 7.8119% from 13.5381%, the average sensitivity

16 enhances 5.7262%.

Chapter 4 14 percent Ge of SiGe nanowire sensors

4.1 Cross-section view : 14 percent Ge of SiGe nanowires

Si⁸⁶Ge¹⁴ nanowires were also successfully fabricated by sidewall spacer formation. Fig.

4-1 is the SEM images of Si⁸⁶Ge¹⁴. The height is about 196 nm and the width is about 80 nm. The Si⁹³Ge⁷ nanowire is p-type which is doped BF², 10¹⁵ ions/cm² and implantation energy is 50KeV.

4.2 Defined sensitivity after dipped APTMS

We select that the current at V^D = -8V is a baseline. For example, the length of Si⁸⁶Ge¹⁴ nanowire is 6um. Before dipped APTMS, the current is -262.25uA at V^D= -8V;

after dipped APTMS, the current change to -249.87uA. Therefore, sensitivity is : S=∣[(-249.87uA)-(-262.25uA)] / (-262.25uA)∣= 4.721% , shown in Fig. 4-2.

4.3 Sensitivity is independent of parallel connection number of nanowires

Here, we discuss parallel connection number of nanowires affect sensitivity. Avearge sensitivity of single、double、quadruple、sextuple and decuple parallel connection number of nanowires is 4.50624%、4.65438%、4.5232%、4.5941% and 4.63955%, respectively, shown as Fig. 4-3.

We can clearly see that the average sensitivity of parallel connection number of nanowires is very close to 4.5%.

Moreover, we take these five average point to do method of least squares , shown as Fig. 4-4. The slope of the line is 8.74125*10^-5. The value is very small and close to a horizontal line. Intercept on y-axis of this line is 4.5433%, and it tells us that average sensitivity is close to 4.5433%.

4.4 Comparing sensitivity between uniform and non-homogeneous SiGe nanowire

Fig. 4-5, shows that oxidizing Si⁸⁶Ge¹⁴ nanowire temperature at 850℃ with 0, 3, 7 and 13 minutes. When nanowire is without oxidation, the average sensitivity is 4.527%.

After oxidation at 850℃ for 3 minutes, the average sensitivity is promoting to 6.0546%.

Adding oxidation time to 7 minutes, the mean sensitivity is increasing to 7.1483%. To go on, adding oxidation time to 13 minutes. However, the average sensitivity is decreasing to 5.1862%. Oxidation time from 0 to 7 minutes, the Ge concentration in outer layer of nanowire is not enough, resulting in sensitivity increasing along with oxidation time.

Nevertheless, oxidation time from 7 to 13 minutes, we guess that defects affect sensitivity mainly; therefore, the average sensitivity decreases.

Adding oxidation temperature to 900℃ with 0, 3, 7 and 13 minutes. Without oxidation, the average sensitivity of Si⁸⁶Ge¹⁴ nanowire is 4.527%. After oxidation at 900℃

for 3 minutes, the average sensitivity is promoting to 6.5694%. Continuing oxidation, when oxidation at 900℃ for 7 minutes, the average sensitivity is promoting to 9.0962%.

However, oxidation at 900℃ for 13 minutes, the average sensitivity is degrading to 9.0962%. This trend is as same as above data. From 0 to 7 minutes, average sensitivity

increases along with time, and from 7 to 13 minutes, average sensitivity degrades, shown as Fig. 4-6.

When Si⁸⁶Ge¹⁴ nanowire is no oxidizing, the Ge concentration distribution to Si ratio is close to 14%, shown in Fig. 4-7. After oxidation at 900℃ for 7 minutes, the surface of Si⁸⁶Ge¹⁴ nanowire, Ge concentration to Si concentration ratio is close to 20%, shown in Fig.

4-8. Moreover, Fig. 4-9 shows that after oxidation at 900℃ for 13 minutes, the surface of Si⁸⁶Ge¹⁴ nanowire, Ge concentration to Si concentration ratio is close to 24%. From Fig.

4-7 to Fig. 4-9, we can clearly know that the Ge concentration is piling up on surface which means outer layer of Si⁸⁶Ge¹⁴ nanowire along with oxidation time.

Via Fig. 4-5 and Fig. 4-6, we can get that higher temperature makes higher sensitivity from 0 to 7 minutes. Higher temperature provides higher energy, letting Ge is easier piling up in the outer layer of SiGe nanowire than lower temperature.

In these conditions, we can get that the best condition is oxidation at 900℃ for 7 minutes, and its sensitivity is 9.0962%. Comparing with no oxidation, Si⁸⁶Ge¹⁴, whose sensitivity is 4.527%. Subtracting 4.527% from 9.0962%, the average sensitivity enhances 4.5692%, shown in Fig. 4-10.

Chapter 5 Conclusions and Future work

Via Ge condensation technique, we successfully performs non-homogeneous SiGe nanowire. Via a series of experiments, we prove that non-homogeneous SiGe nanowire has better sensitivity than uniform SiGe nanowire.

Nevertheless, when oxidation temperature is too high or oxidation time is too long, the sensitivity will decrease. Molecular weight of Ge and Si is very different, when Ge piles up, the interface between Ge and SiO² generates amount of defects. Defects make APTMS binding ability degrading, so sensitivity decreases.

If oxidation temperature or oxidation time is not enough, affecting Ge concentration not sufficient, thus sensitivity decreases, because we cannot confine most current flowing through outer layer of nanowire.

Thus, we need appropriate oxidation temperature and time to get best sensitivity.

No matter how number of parallel connection nanowire is, the sensitivity is very close.

In the future, we can discuss that the defects affect sensitivity. Moreover, we need to investigate the concentration of APTMS versus sensitivity and when we measure I^D-V^D curve, different temperatures affect sensitivity.

Fig. 1-1. (A) Schematic illustrating the conversion of a NWFET into NW pH sensor, (B) Real-time response of an APTES-modified SiNW for pHs from 2 to 9, (C) Plot of the conductance versus pH, and (D) The conductance of unmodified SiNW versus pH (After Y.C. et al, Ref. [1]).

Fig. 1-2. (A) Schematic illustrating a biotin-modified SiNW (left) and subsequent binding of streptavidin to the SiNW surface (right), (B) The conductance increases by positive biotin adsorption. However, the chemical link is irreversible, and (C) The unchanged-conductance is found because of unmodified (After Y.C. et al, Ref.

[1]).

Fig. 1-3. Modification scheme of the SiNW surface for the DNA detector:(1) self-assembly of 3-mercaptopropyltrimethoxysilane(MPTMS); (2) covalent immobilization of DNA probes; (3) DNA detection based on hybridization between label-free complementary DNA target and the immobilized DNA probes on the SiNW surfaces (After Z.L. et al, Ref. [2]).

Fig. 1-4. (a) The conductance does not change by un-match DNA (b) Conductance of p-type NW increases after matched-DNA modified (c) Conducatance of n-type NW deceases after match-DNA modified (After Z.L. et al, Ref. [2]).

Fig. 1-5. Nanowire-based detection of single virus. (Left) Schematic shows two nanowire devices, 1 and 2, where the nanowires are modified with different antibody receptors. Specific binding of single virus to the receptors on nanowire 2 produce a conductance change (Right) characteristic of the surface change of the virus only in nanowire 2. When the virus unbinds from the surface the conductance return to the baseline value (After F.P. et al, Ref. [3]).

Fig. 1-6. Response of the SnO² nanobelts to CO at a working temperature of 400 ⁰C and 30% RH (After E.C. et al, Ref. [4]).

Fig. 1-7. Measured time-dependent current through an individual CPNM sensor upon exposure to NH³ gas. The nanowire device being tested was about 335 nm in diameter (After H.L. et al, Ref. [6]).

Fig. 1-8. Sensor resistance changes with different H² concentration (After K.T.K. et al, Ref.

[8]).

Fig. 1-9. Schematic illustration: Growth of a silicon crystal by VLS (a) Initial condition with liquid droplet on substrate. (b) Growing crystal with liquid droplet at the tip (After R.S.W. et al, Ref. [10]).

Fig. 1-10. SEM images of Si^1-xGe^x nanowires synthesized at different temperatures: (a) 400

0C (b) 430 ⁰C (c) 450 ⁰C (After S.J.W. et al, Ref. [11]).

Fig. 1-11. TEM images of Si^1-xGe^x nanowires synthesized at different temperatures: (a) 430

0C (b) 450 ⁰C (After S.J.W. et al, Ref. [11]).

Fig. 1-12. Schematic diagram for twin silicon nanowire FET fabrication (After S.D.S. et al, Ref. [12]).

Fig. 1-13. Top view and SEM image of nanowire. Diamter is 10 nm and gate length is 30 nm (After S.D.S. et al, Ref. [12]).

Fig. 1-14. Cross-section SEM image of nanowire. Nanowire diameter is about 10 nm (After S.D.S. et al, Ref. [12]).

Fig. 1-15. Multiplexed electrical detections. NW1 detects PSA; NW2 detects CEA; NW3 detects mucin-1 (After G.Z. et al, Ref. [13]).

Fig. 1-16. Schematic of capacitance measurement setup (After R.T. et al, Ref. [15]).

Fig. 1-17. Mobility of nanowires is relative to the radius and V^GS (After A.C.F. et al, Ref.

[14]).

Fig. 1-18. Nanowire field-effect transistor sensors’ sensing mechanism (After F.P. et al, Ref. [19]).

Fig. 1-19. The saturation currents of both short-channel N and P MOSFETs are improved with the use of the SiGe-channel (After Y.C.Y. et al, Ref. [21]).

Fig. 1-20. Procedure for the strained Si on the SGOI structure and Ge profiles (After T.T.

et al, Ref. [22]).

Fig. 1-21. TEM image and Ge profile (After T.T. et al, Ref. [22]).

Fig. 2-1. SiO² layer is grown 5000Å on the Si substrate.

Fig. 2-2. Etching SiO², and the height is about 3000Å.

Fig. 2-3. Depositing α- Si 150Å on the SiO² layer.

Fig. 2-4. Depositing SiGe layer on the amorphous Si layer.

Fig. 2-5. Defined nanowire and S/D.

Fig. 2-6. Etching two side parallel nanowires.

Fig. 2-7. Defined Al contact pad.

Fig. 2-8. APTMS binds silicon oxide layer.

Fig. 3-1. SEM image of Si⁹³Ge⁷ nanowire.

-10 -8 -6 -4 -2 0 2 4 6 8 10

-0.00020 -0.00015 -0.00010 -0.00005 0.00000 0.00005 0.00010 0.00015 0.00020

Current(A)

Voltage(V) 4um normal

4um APTMS

Fig. 3-2. I^D-V^D curve of Si⁹³Ge⁷ nanowire which is 4um long before and after dipped APTMS.

Fig. 3-3. Process of forming non-homogeneous SiGe nanowire with three different temperature and post-annealing at 900℃ in N² ambient for 30 minutes.

Fig. 3-4. Annealing conditions after oxidation (After C.H.T. et al, Ref. [24]).

Fig. 3-5. Sensitivity distribution of oxidation at 850℃ with different time.

Fig. 3-6. Sensitivity distribution of oxidation at 900℃ with different time.

Fig. 3-7. Sensitivity distribution of oxidation at 950℃ with different time.

Fig. 3-8. Sensitivity distribution of oxidation time fixed 3 minutes with different oxidation temperatures.

0 2 4 6 8 10 12 14

Sensitivity(%)

Oxidation Temperature(oC) oxidation time

at 3 minutes

850 900 950

Fig. 3-9. Sensitivity distribution of oxidation time fixed 5 minutes with different oxidation temperatures.

Fig. 3-10. A bar chart of sensitivity distribution with different conditions.

Fig. 4-1. SEM of Si⁸⁶Ge¹⁴ nanowire.

-10 -8 -6 -4 -2 0 2 4 6 8 10

-0.0004 -0.0003 -0.0002 -0.0001 0.0000 0.0001 0.0002 0.0003

Current(A)

Voltage(V) 6um normal

6um APTMS

Fig. 4-2. I^D-V^D curve of Si⁸⁶Ge¹⁴ nanowire which is 6um long before and after dipped APTMS.

Fig. 4-3. Average sensitivity distribution with different parallel connection number of nanowire.

Fig. 4-4. Method of least squares of average sensitivity.

Fig. 4-5. Sensitivity distribution of oxidation at 850℃ with different time.

Fig. 4-6. Sensitivity distribution of oxidation at 900℃ with different time.

Fig. 4-7. Auger analysis of Si⁸⁶Ge¹⁴ nanowire without oxidation.

Fig. 4-8. Auger analysis of Si⁸⁶Ge¹⁴ nanowire at oxidation temperature 900℃ for 7 minutes.

Fig. 4-9. Auger analysis of Si⁸⁶Ge¹⁴ nanowire at oxidation temperature 900℃ for 13 minutes.

Fig. 4-10. A bar chart of sensitivity distribution with different conditions.

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48 簡歷

姓名：鄭文魁性別：男

出生日期：民國 74 年 5 月 16 日出生地：台灣省台南縣

住址：台南縣新營市周武街 79 巷 22 弄 1 號

學歷：興國高級中學 (民國 89 年 9 月~民國 92 年 6 月) 國立高雄大學電機工程學系 (民國 92 年 9 月~民國 96 年 6 月) 國立交通大學電子工程所 (民國 96 年 9 月~民國 98 年 9 月) 碩士論文：應用非均勻矽鍺奈米線在生物感測器上提升其靈敏度

Utilizing Non-Homogeneous SiGe Nanowires to Enhance Sensitivity Obviously in Biosensor

在文檔中應用非均勻矽鍺奈米線在生物感測器上提升其靈敏度 (頁 23-0)